US4740869A - Electrolytic capacitor - Google Patents
Electrolytic capacitor Download PDFInfo
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- US4740869A US4740869A US06/930,415 US93041586A US4740869A US 4740869 A US4740869 A US 4740869A US 93041586 A US93041586 A US 93041586A US 4740869 A US4740869 A US 4740869A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to an electrolytic capacitor. More particularly, it relates to an electrolytic capacitor wherein a novel electrolyte is used.
- An electrolytic capacitor having a capacitor element prepared by rolling foils of a valve metal such as aluminum together with a separator usually has a structure wherein an electrolyte is impregnated to the capacitor element, and such a capacitor element is accomodated and sealed in a metal casing such as an aluminum casing or in a casing made of a synthetic resin.
- the above-mentioned electrolyte has drawbacks such that it is unstable at a high temperature of 120° C. or higher, and the durability characteristic is not good.
- organic acid-type electrolytes have been used and studied wherein an organic acid having a relatively large molecular weight or its salt is used as a solute.
- the solute for an organic acid-type electrolyte for a medium to high voltage capacitor it is known to use, for example, 1,6-decanedicarboxylic acid (Japanese Examined Patent Publication No. 13293/1975 for "Electrolyte for Electrolytic Capacitor") or its salt.
- 1,6-decanedicarboxylic acid Japanese Examined Patent Publication No. 13293/1975 for "Electrolyte for Electrolytic Capacitor"
- the solute itself reacts with the aluminum foils constituting the capacitor element, to form a complex, whereby the initial capacitance is low, and further, in the high temperature life tests or in the high temperature storage tests, a sharp decrease in the capacitance and a considerable increase in the leakage current are observed.
- Another object of the present invention is to provide an electrolytic capacitor wherein a novel electrolyte is employed.
- a further object of the present invention is to substantially lower the specific resistance of the electrolyte and thereby to reduce the tangent of loss angle and the impedance at high frequency of the electrolytic capacitor, and to provide an electrolytic capacitor which is capable of suppressing the change in the capacitance and the increase in the leakage current and which is durable and reliable even at a high temperature.
- the present invention provides an electrolytic capacitor comprising a capacitor element and an electrolyte impregnated to the element, wherein the electrolyte contains a fluorocarboxylic acid or its salt as a solute dissolved in an organic solvent.
- a solution of a fluorocarboxylic acid or its salt in an organic solvent is used.
- the fluorocarboxylic acid or its salt may preferably be a perfluorodibasic acid represented by the general formula C n F 2n (COOH) 2 wherein n is preferably from 1 to 12, more preferably from 2 to 6, or its salt, or a perfluoromonobasic acid represented by the general formula C n F 2n+1 COOH wherein n is as defined above, or its salt.
- R is a lower alkyl group, or its salt.
- the perfluoro group such as C n F 2n or C n F 2n+1 , may be a straight chain type or a branched chain type.
- the salts of the above carboxylic acids may preferably be ammonium salts, quaternary ammonium salts, amine salts or alkali metal salts. Among them, ammonium salts and quaternary ammonium salts are particularly preferred as they provide high conductivity.
- fluorocarboxylic acid or its salt there may be mentioned perfluoromalonic acid, perfluorosuccinic acid, perfluoroglutaric acid, perfluoroadipic acid, perfluorodecanedicarboxylic acid, perfluoropimelic acid, perfluorosuberic acid, trifluoroacetic acid, perfluoropelargonic acid, perfluoroundecylic acid or their salts.
- the fluorocarboxylic acid or its salt may be used, if necessary, in combination with other solutes to form an electrolyte.
- other solutes a hydrocarbon carboxylic acid or its salt, an aromatic carboxylic acid or its salt, and an inorganic acid or its salt, may be mentioned as preferred examples.
- the above-mentioned hydrocarbon carboxylic acid or its salt may preferably be a dibasic acid of the formula C n H 2n (COOH) 2 wherein n is preferably from 1 to 12, more preferably from 2 to 10, or its salt, or a monobasic acid of the formula C n H 2n+1 COOH wherein n is as defined above, or its salt.
- n preferably from 1 to 12, more preferably from 2 to 10, or its salt
- n preferably from 1 to 12, more preferably from 2 to 10, or its salt
- n preferably from 1 to 12, more preferably from 2 to 10, or its salt
- n preferably from 1 to 12
- n preferably from 2 to 10
- a monobasic acid of the formula C n H 2n+1 COOH wherein n is as defined above, or its salt As the salt, an alkali metal salt, an amine salt, an ammonium salt or a quaternary ammonium salt may be mentioned. Particularly preferred is an ammonium salt or a
- hydrocarbon carboxylic acid or its salt examples include 1,6-decanedicarboxylic acid, 1,10-decanedicarboxylic acid, caproic acid, pivalic acid, adipic acid, caprylic acid, pyromellitic acid, and their salts.
- aromatic carboxylic acid includes benzoic acid, toluic acid, p-hydroxybenzoic acid, phthalic acid, salicylic acid, pyromellitic acid and a halobenzoic acid.
- the above-mentioned inorganic acid includes boric acid, heteropoly-acid, metatungstic acid and paratungstic acid.
- the organic solvent for the electrolyte of the present invention is preferably an organic polar solvent.
- any organic polar solvent which is commonly employed for an electrolyte may be used.
- Preferred solvents include amides, lactones, glycols, sulfur compounds and carbonates. Particularly preferred examples include propyl carbonate, dimethylformamide, N-methylformamide, butyrolactone, N-methylpyrrolidone, dimethylsulfoxide, ethylene cyanohydrin, ethylene glycol, and a mono- or di-alkyl ether of ethylene glycol.
- the concentration (content) of the fluorocarboxylic acid or its salt in the electrolyte of the present invention is preferably from 1 to 70% by weight, more preferably from 5 to 60% by weight.
- the amount of such other solutes is selected depending upon the type of such solutes. Usually, such other solutes are used preferably in an amount of from 1 to 50% by weight, more preferably from 5 to 40% by weight in the electrolyte.
- the fluorocarboxylic acid is preferably in an amount of from 0.1 to 5% by weight, more preferably from 0.1 to 2% by weight, in the electrolyte, to obtain particularly excellent effects.
- the electrolyte in the electrolytic capacitor of the present invention is preferably adjusted to have a pH of from 4 to 8, more preferably from 5 to 7, for the prevention of corrosion of the electrode foils.
- the pH of the electrolyte may be adjusted with an alkali, as the case requires.
- an alkali source ammonia or an alkyl amine may suitably be employed.
- Ammonia is most preferred as it provides a sufficiently high conductivity and sparking voltage.
- Ammonia may be incorporated in the form of aqueous ammonia. However, it is preferred to incorporate it in the form of ammonium fluorocarboxylate or ammonium hydrocarbon carboxylate, whereby the control of water content can readily be effected.
- the water content in the electrolyte is as small as possible from the viewpoint of the durability of the electrolytic capacitor, and is usually within the range of from 0.5 to 20% by weight.
- the water content is preferably at most 5% by weight.
- the electrolytic capacitor of the present invention includes various types of capacitors.
- an aluminum foil anode and an aluminum foil cathode separated by a suitable separator such as paper, are used, and they are rolled into a cylindrical shape to obtain a capacitor element, and an electrolyte is impregnated to this capacitor element.
- the amount of the impregnated electrolyte is preferably from 50 to 300% by weight relative to the separator.
- the capacitor element impregnated with the electrolyte is accomodated and sealed in a casing made of a corrosion resistant metal such as aluminum or of a synthetic resin.
- a phosphate, a boric acid, a polyhydric alcohol, etc. may be added to the electrolyte of the present invention, as chemical improvers, as the case requires.
- adipic acid HOOCCH 2 CH 2 CH 2 CH 2 COOH
- aqueous ammonia was added to adjust the solution to pH6.
- This electrolyte contained 3.1% of water.
- an electrolyte was prepared in the same manner as above except that 115 g of decanedicarboxylic acid (HOOC(CH 2 ) 10 COOH) was used.
- An electrolyte was prepared in the same manner as in Example 1 except that perfluoroglutaric acid (HOOCCF 2 CF 2 CF 2 COOH) was used instead of perfluoroadipic acid, and an aqueous sodium hydroxide solution was used instead of aqueous ammonia.
- This electrolyte contained 4.4% by weight of water.
- an electrolyte was prepared in the same manner as in Comparative Example 1 except that glutaric acid was used instead of adipic acid, and an aqueous sodium hydroxide solution was used instead of aqueous ammonia. This electrolyte contained 4.0% by weight of water.
- capacitors prescribed for 470 ⁇ F/200 V D.C. were prepared, and subjected to high temperature life tests at 105° C. for 2000 hours at the working voltage, and to high temperature storage tests at 105° C. for 1000 hours. The results are shown in Tables 4 and 5, respectively.
- Electrolytes of the present invention prepared by dissolving the 1,6-decanedicarboxylic acid or its salt as the main component in an organic polar solvent, followed by an addition of a fluorocarboxylic acid, are presented in Table 6 together with Comparative Examples.
- the compositions of the electrolytes are indicated by % by weight, and the specific resistance ( ⁇ cm) is the one measured at an electrolyte temperature of 20° C. Further, the spark voltage was the one measured at 85° C.
- electrolytic capacitors (prescribed for 10 ⁇ F/400 V D.C.) were prepared. Twenty samples of each capacitor were subjected to a high temperature life test at a temperature of 105° C. for 1000 hours at the working voltage. The results are shown in Table 7. Further, electrolytic capacitors (prescribed for 200 ⁇ F/400 V D.C.) were subjected to a high temperature storage test at 105° C. for 1000 hours. The results are shown in Table 8. Each value for the initial properties and the properties after the test is an average value of 20 samples of each electrolytic capacitor.
- the decrease in capacitance in the Comparative Examples 5-1 and 5-2 shown in Tables 7 and 8, are attributable to the fact that 1,6-decanedicarboxylic acid in the electrolyte reacts with the aluminum foils constituting the capacitor element to result in the remarkable decrease of the surface area.
- the increase in the leakage current is attributable to the fact that 1,6-decanedicarboxylic acid reacts with the aluminum anode oxide film as a dielectric material to form an unstable aluminum complex film, which will be dissolved in the electrolyte at a high temperature, whereby the leakage current increases.
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Abstract
An electrolytic capacitor comprising a capacitor element and an electrolyte impregnated to the element, wherein the electrolyte contains a flurorocarboxylic acid or its salt as a solute dissolved in an organic solvent.
Description
The present invention relates to an electrolytic capacitor. More particularly, it relates to an electrolytic capacitor wherein a novel electrolyte is used.
An electrolytic capacitor having a capacitor element prepared by rolling foils of a valve metal such as aluminum together with a separator, usually has a structure wherein an electrolyte is impregnated to the capacitor element, and such a capacitor element is accomodated and sealed in a metal casing such as an aluminum casing or in a casing made of a synthetic resin.
It is known to employ, as an electrolyte for the electrolytic capacitor, a solution obtained by dissolving an organic acid or organic acid salt such as adipic acid or ammonium adipate in a polar solvent such as glycerol or ethylene glycol. (See e.g. Japanese Examined Patent Publication No. 13019/1983 or Japanese Unexamined Patent Publication No. 159321/1983.)
However, the above-mentioned electrolyte has drawbacks such that it is unstable at a high temperature of 120° C. or higher, and the durability characteristic is not good.
For high temperature electrolytic capacitors, organic acid-type electrolytes have been used and studied wherein an organic acid having a relatively large molecular weight or its salt is used as a solute.
As the solute for an organic acid-type electrolyte for a medium to high voltage capacitor, it is known to use, for example, 1,6-decanedicarboxylic acid (Japanese Examined Patent Publication No. 13293/1975 for "Electrolyte for Electrolytic Capacitor") or its salt. In the electrolytic capacitor wherein the electrolyte containing 1,6-decanedicarboxylic acid is used, the solute itself reacts with the aluminum foils constituting the capacitor element, to form a complex, whereby the initial capacitance is low, and further, in the high temperature life tests or in the high temperature storage tests, a sharp decrease in the capacitance and a considerable increase in the leakage current are observed. Thus, such a capacitor is incapable of satisfying the requirements for a high performance electrolytic capacitor. For this reason, it has been proposed to incorporate maleic acid (Japanese Unexamined Patent Publication No. 92208/1983 "Electrolyte for Electrolytic Capacitor") or citric acid (Japanese Unexamined Patent Publication No. 219920/1984 "Electrolyte for Electrolytic Capacitor") as an additive to 1,6-decanedicarboxylic acid. Such a proposal has a drawback that the electrolyte is still poor in the thermal stability.
It is an object of the present invention to overcome the above-mentioned drawbacks inherent to the conventional techniques.
Another object of the present invention is to provide an electrolytic capacitor wherein a novel electrolyte is employed.
A further object of the present invention is to substantially lower the specific resistance of the electrolyte and thereby to reduce the tangent of loss angle and the impedance at high frequency of the electrolytic capacitor, and to provide an electrolytic capacitor which is capable of suppressing the change in the capacitance and the increase in the leakage current and which is durable and reliable even at a high temperature.
The present invention provides an electrolytic capacitor comprising a capacitor element and an electrolyte impregnated to the element, wherein the electrolyte contains a fluorocarboxylic acid or its salt as a solute dissolved in an organic solvent.
Now, the present invention will be described in detail with reference to the preferred embodiments.
In the present invention, a solution of a fluorocarboxylic acid or its salt in an organic solvent is used. The fluorocarboxylic acid or its salt may preferably be a perfluorodibasic acid represented by the general formula Cn F2n (COOH)2 wherein n is preferably from 1 to 12, more preferably from 2 to 6, or its salt, or a perfluoromonobasic acid represented by the general formula Cn F2n+1 COOH wherein n is as defined above, or its salt. Further, it is possible to employ a perfluorocarboxylic acid polymer soluble in an organic solvent obtained by hydrolysing a copolymer of CF2 ═CF2 with CF═CFO(CF2)1-12 COOR wherein R is a lower alkyl group, or its salt. Particularly good results are obtainable when a perfluorodicarboxylic acid or its salt is used among them. The perfluoro group such as Cn F2n or Cn F2n+1, may be a straight chain type or a branched chain type.
The salts of the above carboxylic acids may preferably be ammonium salts, quaternary ammonium salts, amine salts or alkali metal salts. Among them, ammonium salts and quaternary ammonium salts are particularly preferred as they provide high conductivity.
As preferred examples of the fluorocarboxylic acid or its salt, there may be mentioned perfluoromalonic acid, perfluorosuccinic acid, perfluoroglutaric acid, perfluoroadipic acid, perfluorodecanedicarboxylic acid, perfluoropimelic acid, perfluorosuberic acid, trifluoroacetic acid, perfluoropelargonic acid, perfluoroundecylic acid or their salts.
The fluorocarboxylic acid or its salt may be used, if necessary, in combination with other solutes to form an electrolyte. As such other solutes, a hydrocarbon carboxylic acid or its salt, an aromatic carboxylic acid or its salt, and an inorganic acid or its salt, may be mentioned as preferred examples.
The above-mentioned hydrocarbon carboxylic acid or its salt may preferably be a dibasic acid of the formula Cn H2n (COOH)2 wherein n is preferably from 1 to 12, more preferably from 2 to 10, or its salt, or a monobasic acid of the formula Cn H2n+1 COOH wherein n is as defined above, or its salt. As the salt, an alkali metal salt, an amine salt, an ammonium salt or a quaternary ammonium salt may be mentioned. Particularly preferred is an ammonium salt or a quaternary ammonium salt.
Preferred examples of the above-mentioned hydrocarbon carboxylic acid or its salt, include 1,6-decanedicarboxylic acid, 1,10-decanedicarboxylic acid, caproic acid, pivalic acid, adipic acid, caprylic acid, pyromellitic acid, and their salts.
The above-mentioned aromatic carboxylic acid includes benzoic acid, toluic acid, p-hydroxybenzoic acid, phthalic acid, salicylic acid, pyromellitic acid and a halobenzoic acid.
Likewise, the above-mentioned inorganic acid includes boric acid, heteropoly-acid, metatungstic acid and paratungstic acid.
The organic solvent for the electrolyte of the present invention is preferably an organic polar solvent. As such a solvent, any organic polar solvent which is commonly employed for an electrolyte, may be used. Preferred solvents include amides, lactones, glycols, sulfur compounds and carbonates. Particularly preferred examples include propyl carbonate, dimethylformamide, N-methylformamide, butyrolactone, N-methylpyrrolidone, dimethylsulfoxide, ethylene cyanohydrin, ethylene glycol, and a mono- or di-alkyl ether of ethylene glycol.
The concentration (content) of the fluorocarboxylic acid or its salt in the electrolyte of the present invention is preferably from 1 to 70% by weight, more preferably from 5 to 60% by weight.
When the fluorocarboxylic acid or its salt is used in combination with other solutes, the amount of such other solutes is selected depending upon the type of such solutes. Usually, such other solutes are used preferably in an amount of from 1 to 50% by weight, more preferably from 5 to 40% by weight in the electrolyte. When used in combination with the hydrocarbon carboxylic acid or its salt, the fluorocarboxylic acid is preferably in an amount of from 0.1 to 5% by weight, more preferably from 0.1 to 2% by weight, in the electrolyte, to obtain particularly excellent effects.
The electrolyte in the electrolytic capacitor of the present invention is preferably adjusted to have a pH of from 4 to 8, more preferably from 5 to 7, for the prevention of corrosion of the electrode foils. The pH of the electrolyte may be adjusted with an alkali, as the case requires. As such an alkali source, ammonia or an alkyl amine may suitably be employed. Ammonia is most preferred as it provides a sufficiently high conductivity and sparking voltage. Ammonia may be incorporated in the form of aqueous ammonia. However, it is preferred to incorporate it in the form of ammonium fluorocarboxylate or ammonium hydrocarbon carboxylate, whereby the control of water content can readily be effected.
The water content in the electrolyte is as small as possible from the viewpoint of the durability of the electrolytic capacitor, and is usually within the range of from 0.5 to 20% by weight. When the capacitor is intended for use at a high temperature for a long period time, the water content is preferably at most 5% by weight.
The electrolytic capacitor of the present invention includes various types of capacitors. In a typical type, an aluminum foil anode and an aluminum foil cathode separated by a suitable separator such as paper, are used, and they are rolled into a cylindrical shape to obtain a capacitor element, and an electrolyte is impregnated to this capacitor element. The amount of the impregnated electrolyte is preferably from 50 to 300% by weight relative to the separator. The capacitor element impregnated with the electrolyte is accomodated and sealed in a casing made of a corrosion resistant metal such as aluminum or of a synthetic resin.
Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to these specific Examples, and various changes or modifications may be made within the scope of the present invention. For instance, in a case where a 1,6-decanedicarboxylic acid salt or a fluorocarboxylic acid salt is used, such a salt may be added by itself in an organic polar solvent, or it may be added in the form of a raw material or substance which is capable of being converted to such a salt.
Further, other substances may be added within the respective ranges not to impair the object of the present invention.
For instance, a phosphate, a boric acid, a polyhydric alcohol, etc. may be added to the electrolyte of the present invention, as chemical improvers, as the case requires.
72.5 g of a perfluoroadipic acid (HOOCCF2 CF2 CF2 CF2 COOH) was dissolved in 500 g of ethylene glycol, and aqueous ammonia was added to adjust the solution to pH6. This electrolyte contained 4.2% by weight of water.
On the other hand, 36.5 g of adipic acid (HCOOCCH2 CH2 CH2 CH2 COOH) was dissolved in 500 g of ethylene glycol, and aqueous ammonia was added to adjust the solution to pH6. This electrolyte contained 3.1% of water.
Each electrolyte was sealed in a container and maintained at 125° C., and the change in the specific resistance of the electrolyte was examined. The results are shown in Table 1.
TABLE 1
______________________________________
Specific resistance (Ωcm, 40° C.)
Time (hrs.) kept
Perfluoroadipic acid
Adipic acid
at 125° C.
system system
______________________________________
0 150 206
1000 155 476
2000 158 609
______________________________________
It is evident from Table 1 that the change in the specific resistance is smaller and the stability at a high temperature is higher in the case where the perfluoroadipic acid was used. EXAMPLE 2 AND COMPARATIVE EXAMPLE 2
295 g of perfluorodecanedicarboxylic acid (HOOC(CF2)10 COOH) was dissolved in 500 g of ethylene glycol, and a 10 wt. % tetramethylammonium hydroxide aqueous solution was added to adjust the solution to pH6. This solution was heated for evaporation of water to adjust the water content to 1.5% by weight.
On the other hand, an electrolyte was prepared in the same manner as above except that 115 g of decanedicarboxylic acid (HOOC(CH2)10 COOH) was used.
By using each electrolyte, the relation between the time kept at 125° C. and the specific resistance, was obtained in the same manner as in Example 1. The results are shown in Table 2.
TABLE 2
______________________________________
Specific resistance (Ωcm, 40° C.)
Decanedi-
Time (hrs.) kept
Perfluorodecanedi-
carboxylic acid
at 125° C.
carboxylic acid system
system
______________________________________
0 480 546
1000 482 610
2000 485 680
______________________________________
It is evident from Table 2 that the change in the specific resistance is smaller and the stability at a high temperature is higher in the case where the perfluorodecanedicarboxylic acid was used. EXAMPLE 3 AND COMPARATIVE EXAMPLE 3
An electrolyte was prepared in the same manner as in Example 1 except that perfluoroglutaric acid (HOOCCF2 CF2 CF2 COOH) was used instead of perfluoroadipic acid, and an aqueous sodium hydroxide solution was used instead of aqueous ammonia. This electrolyte contained 4.4% by weight of water.
On the other hand, an electrolyte was prepared in the same manner as in Comparative Example 1 except that glutaric acid was used instead of adipic acid, and an aqueous sodium hydroxide solution was used instead of aqueous ammonia. This electrolyte contained 4.0% by weight of water.
By using each electrolyte, the relation between the time kept at 125° C. and the specific resistance was obtained in the same manner as in Example 1. The results are shown in Table 3.
TABLE 3
______________________________________
Specific resistance (Ωcm, 40° C.)
Time (hrs.) kept
Perfluoroglutaric
Gultaric acid
at 125° C.
acid system system
______________________________________
0 201 317
1000 205 420
2000 203 440
______________________________________
It is evident from Table 3 that the stability at a high temperature is higher in the case where the perfluoroglutaric acid was used.
Electrolytes identified below by Comparative Examples 4-1 to 4-4 and electrolytes identified below by Examples 4-1 to 4-4 wherein the acids used in the Comparative Examples were replaced by perfluorodicarboxylic acids, respectively, were prepared. By using these electrolytes, capacitors prescribed for 470 μF/200 V D.C. were prepared, and subjected to high temperature life tests at 105° C. for 2000 hours at the working voltage, and to high temperature storage tests at 105° C. for 1000 hours. The results are shown in Tables 4 and 5, respectively.
______________________________________ Comparative Example 4-1 Ammonium benzoate 9 Benzoic acid 3 Water 3 Ethylene glycol 85 Example 4-1 Ammonium benzoate 9 Perfluoroglutaric acid 3 Water 3 Ethylene glycol 85 Comparative Example 4-2 Ammonium p-toluylate 9 p-Toluylic acid 3 Water 3 Ethylene glycol 85 Example 4-2 Ammonium p-toluylate 9 Perfluoroadipic acid 3 Water 3 Ethylene glycol 85 Comparative Example 4-3 Ammonium caproate 6 Carproic acid 5 Water 3 Ethylene glycol 86 Example 4-3 Ammonium caproate 6 Perfluorosuberic acid 5 Water 3 Ethylene glycol 86 Comparative Example 4-4 Ammonium pivalate 6 Pivalic acid 5 Water 3 Ethylene glycol 86 Example 4-4 Ammonium pivalate 6 Perfluorosebacic acid 5 Water 3 Ethylene glycol 86 ______________________________________
TABLE 4
__________________________________________________________________________
High temperature life test (105° C. for 2000 hrs.)
Properties after the
Initial properties
test
Tangent
Leakage
Change (%)
Tangent
Leakage
Capacitance
of loss
current
in the
of loss
current
(μF)
angle
(μA)
capacitance
angle
(μA)
__________________________________________________________________________
Comparative
460 0.039
30.1 -5.8 0.048
22.2
Example 4-1
Example 4-1
472 0.034
25.6 -3.0 0.038
18.5
Comparative
465 0.040
30.3 -5.2 0.049
23.3
Example 4-2
Example 4-2
469 0.035
24.9 -3.1 0.040
18.6
Comparative
470 0.043
35.8 -20.8 0.071
25.3
Example 4-3
Example 4-3
473 0.037
26.6 -5.1 0.044
20.2
Comparative
461 0.040
36.1 -18.4 0.066
24.7
Example 4-4
Example 4-4
468 0.034
28.2 -4.1 0.042
19.6
__________________________________________________________________________
TABLE 5
__________________________________________________________________________
High temperature storage test (105° C. for 1000 hrs.)
Properties after of
Initial properties
test
Tangent
Leakage
Change (%)
Tangent
Leakage
Capacitance
of loss
current
in the
of loss
current
(μF)
angle
(μA)
capacitance
angle
(μA)
__________________________________________________________________________
Comparative
466 0.039
33.5 -2.7 0.042
310
Example 4-1
Example 4-1
471 0.033
25.8 -2.1 0.035
120
Comparative
468 0.039
30.8 -3.1 0.043
330
Example 4-2
Example 4-2
475 0.035
26.1 -1.9 0.038
110
Comparative
460 0.044
36.2 -12.3 0.064
1200
Example 4-3
Example 4-3
471 0.037
25.7 -4.1 0.041
280
Comparative
469 0.040
35.8 -10.7 0.058
1310
Example 4-4
Example 4-4
466 0.034
21.1 -3.7 0.039
290
__________________________________________________________________________
It is evident from the results of Tables 4 and 5 that by substituting perfluorocarboxylic acids for carboxylic acids, it is possible to suppress the changes in the properties, particularly the increase of the leakage current in the storage tests and the change in the capacitance.
Electrolytes of the present invention prepared by dissolving the 1,6-decanedicarboxylic acid or its salt as the main component in an organic polar solvent, followed by an addition of a fluorocarboxylic acid, are presented in Table 6 together with Comparative Examples. The compositions of the electrolytes are indicated by % by weight, and the specific resistance (Ωcm) is the one measured at an electrolyte temperature of 20° C. Further, the spark voltage was the one measured at 85° C.
TABLE 6
______________________________________
Electrolyte Compositions
Specific Spark
Electrolyte compositions
resistance
voltage
(wt %) (Ωcm)
(V)
______________________________________
Compara-
1,6-Decanedicarboxylic
15 580 435
tive acid
Example Aqueous ammonia 4.5
5-1 Maleic aid 0.2
Ethylene glycol 80.3
Compara-
1,6-Decanedicarboxylic
15 580 430
tive acid
Example Aqueous ammonia 4.5
5-2 Citric acid 0.2
Ethylene glycol 80.3
Example 1,6-Decanedicarboxylic
15 470 440
5-1 acid
Aqueous ammonia 4.5
Perfluoromalonic 0.3
acid
Ethylene glycol 80.2
Example 1,6-Decanedicarboxylic
13 480 450
5-2 acid
1,10-Decanedicarboxylic
2
acid
Aqueous ammonia 4.5
Perfluorosuccinic
0.3
acid
Ethylene glycol 80.2
Example 1,6-Decanedicarboxylic
10 480 450
5-3 acid
1,10-Decanedicarboxylic
1
acid
5,6-Decanedicarboxylic
4
acid
Aqueous ammonia 4.5
Perfluoroglutaric
0.3
acid
Ethylene glycol 80.2
Example 1,6-Decanedicarboxylic
10 460 445
5-4 acid
1,10-Decanedicarboxylic
1
acid
5,6-Decanedicarboxylic
4
acid
Aqueous ammonia 4.5
Perfluoroadipic 0.3
acid
Ethylene glycol 80.2
Example 1,6-Decanedicarboxylic
15 490 450
5-5 acid
Isopropyl amine 2
Perfluoropimelic 0.3
acid
Ethylene glycol 82.7
Example 1,6-Decanedicarboxylic
12 500 450
5-6 acid
1,10-Decanedicarboxylic
4
acid
Aqueous ammonia 3
Perfluorosuberic 0.3
acid
Ethylene glycol 65
Diethylene glycol
15.7
Example 1,6-Decanedicarboxylic
15 475 440
5-7 acid
Aqueous ammonia 4.5
Trifluoroacetic 0.3
acid
Ethylene glycol 80.2
Example 1,6-Decanedicarboxylic
13 480 450
5-8 acid
1,10-Decanedicarboxylic
2
acid
Aqueous ammonia 4.5
Perfluoropelargonic
0.3
acid
Ethylene glycol 80.2
Example 1,6-Decanedicarboxylic
10 460 450
5-9 acid
1,10-Decanedicarboxylic
1
acid
5,6-Decanedicarboxylic
4
acid
Aqueous ammonia 4.5
Perfluoroundecylic
0.3
acid
Ethylene glycol 80.2
______________________________________
By using electrolytes of Comparative Examples 5-1 and 5-2 and Examples 5-2, 5-4 and 5-8 among the electrolytes shown in Table 6, electrolytic capacitors (prescribed for 10 μF/400 V D.C.) were prepared. Twenty samples of each capacitor were subjected to a high temperature life test at a temperature of 105° C. for 1000 hours at the working voltage. The results are shown in Table 7. Further, electrolytic capacitors (prescribed for 200 μF/400 V D.C.) were subjected to a high temperature storage test at 105° C. for 1000 hours. The results are shown in Table 8. Each value for the initial properties and the properties after the test is an average value of 20 samples of each electrolytic capacitor.
TABLE 7
__________________________________________________________________________
Comparison of properties (10 μF/400 V D.C.)
Properties after the
high temperature
Initial properties
life test
Tangent
Leakage
Change (%)
Tangent
Leakage
Capacitance
of loss
current
in the
of loss
current
(μF)
angle
(μA)
capacitance
angle
(μA)
__________________________________________________________________________
Comparative
9.8 0.050
1.0 -7.0 0.060
1.0
Example 5-1
Comparative
9.5 0.048
0.9 -9.2 0.065
0.9
Example 5-2
Example 5-2
10.8 0.044
0.8 -2.8 0.047
0.7
Example 5-4
10.6 0.046
0.9 -3.4 0.052
0.8
Example 5-8
10.8 0.046
0.9 -3.5 0.053
0.7
__________________________________________________________________________
TABLE 8
__________________________________________________________________________
Comparison of properties (220 μF/400 V D.C.)
Properties after the
high temperature
Initial properties storage test
Tangent
Leakage
Impedance
Change (%)
Tangent
Leakage
Capacitance
of loss
current
(Ω)
in the
of loss
current
(μF)
angle
(μA)
100 KHz
capacitance
angle
(μA)
__________________________________________________________________________
Comparative
215 0.050
30.2 0.17 -6.5 0.065
1280
Example 5-1
Comparative
208 0.048
18.2 0.15 -8.2 0.068
1050
Example 5-2
Example 5-2
230 0.041
10.5 0.10 -1.6 0.044
380
Example 5-4
228 0.043
10.8 0.11 -2.0 0.049
420
Example 5-8
231 0.042
10.7 0.11 -2.2 0.048
450
__________________________________________________________________________
It is evident from Tables 7 and 8 that in Comparative Examples 5-1 and 5-2, the initial values of capacitance are lower by about 5% relative to the prescribed value, and the changes in the capacitance after the tests are substantial. Further, as is evident from Table 8, in Comparative Examples 5-1 and 5-2, the leakage currents are substantial when they are compared with Examples 5-2, 5-4 and 5-8.
The decrease in capacitance in the Comparative Examples 5-1 and 5-2 shown in Tables 7 and 8, are attributable to the fact that 1,6-decanedicarboxylic acid in the electrolyte reacts with the aluminum foils constituting the capacitor element to result in the remarkable decrease of the surface area. The increase in the leakage current is attributable to the fact that 1,6-decanedicarboxylic acid reacts with the aluminum anode oxide film as a dielectric material to form an unstable aluminum complex film, which will be dissolved in the electrolyte at a high temperature, whereby the leakage current increases.
On the other hand, by the addition of a fluorocarboxylic acid to the solute composed mainly of 1,6-decanedicarboxylic acid or its salt, the formation of the complex of 1,6-decanedicarboxylic acid is suppressed. Further, by lowering the specific resistance, the tangent of loss angle or the impedance at a high frequency, can be suppressed to a low level.
Claims (12)
1. An electrolytic capacitor comprising a capacitor element and an electrolyte impregnated to the element, wherein the electrolyte contains a perfluorodicarboxylic acid having from 1 to 12 carbon atoms or a salt thereof as a solute dissolved in an organic solvent.
2. The electrolytic capacitor according to claim 1, wherein the perflouorodicarboxylic acid salt is an alkali metal salt, an amine salt, an ammonium salt, or a quaternary ammonium salt.
3. The electrolytic capacitor according to claim 1, wherein the electrolyte contains a hydrocarbon caboxylic acid or its salt as an additional solute.
4. The electrolytic capacitor according to claim 3, wherein the hydrocarbon carboxylic acid is a monobasic or dibasic acid having from 2 to 15 carbon atoms.
5. The electrolytic capacitor according to claim 3, wherein the hydrocarbon carboxylic acid salt is an alkali metal salt, an amine salt, an ammonium salt, or a quaternary ammonium salt.
6. The electrolytic capacitor according to claim 3, wherein the content of the hydrocarbon carboxylic acid or its salt in the electrolyte is from 1 to 50% by weight,
7. The electrolytic capacitor according to claim 1, wherein the organic solvent is an organic polar solvent.
8. The electrolytic capacitor according to claim 7 wherein the organic polar solvent is ethylene glycol and/or γ-butyl lactone.
9. The electrolytic capacitor according to claim 7, wherein the content of the perfluorodicarboxylic acid or its salt in the electrolyte is from 0.1 to 5% by weight.
10. The electrolytic capacitor according to claim 1, wherein the content of the perfluorodicarboxylic acid or its salt in the electrolyte is from 1 to 70% by weight.
11. The electrolytic capacitor according to claim 1, wherein the electrolyte has a pH of from 4 to 8.
12. The electrolytic capacitor according to claim 1, wherein the content of water in the electrolyte is from 0.5 to 20% by weight.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-253661 | 1985-11-14 | ||
| JP25366185A JPS62114208A (en) | 1985-11-14 | 1985-11-14 | Electrolyte for driving electrolytic capacitor |
| JP19266986A JPS6350011A (en) | 1986-08-20 | 1986-08-20 | Electrolytic capacitor driving electrolyte |
| JP60-192669 | 1986-08-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4740869A true US4740869A (en) | 1988-04-26 |
Family
ID=26507462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/930,415 Expired - Fee Related US4740869A (en) | 1985-11-14 | 1986-11-14 | Electrolytic capacitor |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4740869A (en) |
| EP (1) | EP0229254A3 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4914548A (en) * | 1986-10-20 | 1990-04-03 | Yoshiyo Kubo | Electrolytic paper for electrolytic capacitor |
| US5146391A (en) * | 1987-04-30 | 1992-09-08 | Specialised Conductives Pty. Ltd. | Crosslinked electrolyte capacitors and methods of making the same |
| US5585999A (en) * | 1994-09-30 | 1996-12-17 | The United States Of America As Represented By The Secretary Of The Air Force | Supercapacitor electrochemical cell |
| US6134099A (en) * | 1997-06-03 | 2000-10-17 | Matsushita Electric Industrial | Electrolytic capacitor having a conducting polymer layer without containing an organic acid-type dopant |
| US6493211B1 (en) * | 1999-03-17 | 2002-12-10 | Nippon Chemi-Con Corporation | Electrolyte for electrolytic capacitor |
| US20080035880A1 (en) * | 2004-10-25 | 2008-02-14 | Hiroshi Egawa | Antifreeze/coolant composition |
| US8187763B2 (en) | 2003-07-11 | 2012-05-29 | Honda Motor Co., Ltd. | Cooling liquid composition for fuel cell |
| CN113517141A (en) * | 2021-06-29 | 2021-10-19 | 西安交通大学 | A working electrolyte and preparation method for improving hydration resistance of medium and high voltage aluminum electrolytic capacitors |
| CN113517140A (en) * | 2021-06-29 | 2021-10-19 | 西安交通大学 | Working electrolyte for improving hydration resistance of low-voltage aluminum electrolytic capacitor and preparation method thereof |
| CN113517142A (en) * | 2021-06-29 | 2021-10-19 | 西安交通大学 | Manufacturing method of high-specific-volume high-hydration-resistance medium-high voltage aluminum electrolytic capacitor anode forming foil |
| CN113539686A (en) * | 2021-06-29 | 2021-10-22 | 西安交通大学 | Manufacturing method of anode forming foil of high-specific-volume high-hydration-resistance low-voltage aluminum electrolytic capacitor |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0995785A1 (en) * | 1998-10-14 | 2000-04-26 | Texaco Development Corporation | Corrosion inhibitors and synergistic inhibitor combinations for the protection of light metals in heat-transfer fluids and engine coolants |
| WO2002056324A1 (en) * | 2001-01-15 | 2002-07-18 | Ube Industries, Ltd. | Electrolysis solution for electrolytic capacitors |
| US7859828B2 (en) * | 2004-09-07 | 2010-12-28 | Panasonic Corporation | Electrolytic solution for electrolytic capacitor, and electrolytic capacitor using the same |
| CN105473150B (en) | 2013-08-20 | 2019-01-18 | 3M创新有限公司 | Boron-silylated polyether complex compound |
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| US2923867A (en) * | 1956-07-02 | 1960-02-02 | Sprague Electric Co | Electrolytic capacitors |
| US2932153A (en) * | 1957-07-29 | 1960-04-12 | Sprague Electric Co | Electrolytic capacitor and method of making |
| US3676752A (en) * | 1971-03-19 | 1972-07-11 | Sprague Electric Co | Aluminum electrolytic capacitor |
| US3811077A (en) * | 1973-05-04 | 1974-05-14 | Monsanto Co | Liquid impregnated capacitor |
| US3928705A (en) * | 1971-04-15 | 1975-12-23 | Celanese Corp | Dielectric insulation employing open-celled microporous film |
| US4381536A (en) * | 1981-02-02 | 1983-04-26 | Sprague Electric Company | Low voltage electrolytic capacitor |
| US4469610A (en) * | 1983-07-18 | 1984-09-04 | Nippon Chemi-Con Corporation | Electrolyte for an electrolytic capacitor |
-
1986
- 1986-11-11 EP EP86115635A patent/EP0229254A3/en not_active Withdrawn
- 1986-11-14 US US06/930,415 patent/US4740869A/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2923867A (en) * | 1956-07-02 | 1960-02-02 | Sprague Electric Co | Electrolytic capacitors |
| US2932153A (en) * | 1957-07-29 | 1960-04-12 | Sprague Electric Co | Electrolytic capacitor and method of making |
| US3676752A (en) * | 1971-03-19 | 1972-07-11 | Sprague Electric Co | Aluminum electrolytic capacitor |
| US3928705A (en) * | 1971-04-15 | 1975-12-23 | Celanese Corp | Dielectric insulation employing open-celled microporous film |
| US3811077A (en) * | 1973-05-04 | 1974-05-14 | Monsanto Co | Liquid impregnated capacitor |
| US4381536A (en) * | 1981-02-02 | 1983-04-26 | Sprague Electric Company | Low voltage electrolytic capacitor |
| US4469610A (en) * | 1983-07-18 | 1984-09-04 | Nippon Chemi-Con Corporation | Electrolyte for an electrolytic capacitor |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4914548A (en) * | 1986-10-20 | 1990-04-03 | Yoshiyo Kubo | Electrolytic paper for electrolytic capacitor |
| US5146391A (en) * | 1987-04-30 | 1992-09-08 | Specialised Conductives Pty. Ltd. | Crosslinked electrolyte capacitors and methods of making the same |
| US5585999A (en) * | 1994-09-30 | 1996-12-17 | The United States Of America As Represented By The Secretary Of The Air Force | Supercapacitor electrochemical cell |
| US6134099A (en) * | 1997-06-03 | 2000-10-17 | Matsushita Electric Industrial | Electrolytic capacitor having a conducting polymer layer without containing an organic acid-type dopant |
| US6361572B1 (en) | 1997-06-03 | 2002-03-26 | Matsushita Electric Industrial Co., Ltd. | Method of making an electrolytic capacitor having a conductive polymer formed on the inner surface of micropores of the anodes |
| US6493211B1 (en) * | 1999-03-17 | 2002-12-10 | Nippon Chemi-Con Corporation | Electrolyte for electrolytic capacitor |
| US8187763B2 (en) | 2003-07-11 | 2012-05-29 | Honda Motor Co., Ltd. | Cooling liquid composition for fuel cell |
| US20080035880A1 (en) * | 2004-10-25 | 2008-02-14 | Hiroshi Egawa | Antifreeze/coolant composition |
| US7540974B2 (en) | 2004-10-25 | 2009-06-02 | Honda R&D Co, Ltd. | Antifreeze/coolant composition |
| CN113517141A (en) * | 2021-06-29 | 2021-10-19 | 西安交通大学 | A working electrolyte and preparation method for improving hydration resistance of medium and high voltage aluminum electrolytic capacitors |
| CN113517140A (en) * | 2021-06-29 | 2021-10-19 | 西安交通大学 | Working electrolyte for improving hydration resistance of low-voltage aluminum electrolytic capacitor and preparation method thereof |
| CN113517142A (en) * | 2021-06-29 | 2021-10-19 | 西安交通大学 | Manufacturing method of high-specific-volume high-hydration-resistance medium-high voltage aluminum electrolytic capacitor anode forming foil |
| CN113539686A (en) * | 2021-06-29 | 2021-10-22 | 西安交通大学 | Manufacturing method of anode forming foil of high-specific-volume high-hydration-resistance low-voltage aluminum electrolytic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0229254A2 (en) | 1987-07-22 |
| EP0229254A3 (en) | 1987-08-26 |
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Legal Events
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|---|---|---|---|
| AS | Assignment |
Owner name: ELNA COMPANY LTD., NO. 2-1, 2-CHOME, SHINMACHI, TS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:IWANO, NAOTO;SHIMIZU, HIDEO;KOMATSU, SHIGEO;AND OTHERS;REEL/FRAME:004720/0188 Effective date: 19861106 Owner name: ASAHI GLASS COMPANY LTD., CO. 1-2, MARUNOUCHI 2-CH Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:MORIMOTO, TAKESHI;MATSUBARA, TOSHIYA;HAMATANI, YOSHIKI;REEL/FRAME:004720/0191 Effective date: 19861106 |
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